EP2371018B1 - Light extraction film with nanoparticle coatings - Google Patents

Light extraction film with nanoparticle coatings Download PDF

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Publication number
EP2371018B1
EP2371018B1 EP09836641.2A EP09836641A EP2371018B1 EP 2371018 B1 EP2371018 B1 EP 2371018B1 EP 09836641 A EP09836641 A EP 09836641A EP 2371018 B1 EP2371018 B1 EP 2371018B1
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EP
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Prior art keywords
nanoparticles
layer
index
light
substrate
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EP09836641.2A
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German (de)
French (fr)
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EP2371018A2 (en
EP2371018A4 (en
Inventor
Jun-Ying Zhang
Jimmie R. Baran, Jr.
Terry L. Smith
William J. Schultz
William Blake Kolb
Cheryl A. Patnaude
Sergey A. Lamansky
Brian K. Nelson
Naiyong Jing
Brant U. Kolb
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3M Innovative Properties Co
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3M Innovative Properties Co
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/85Arrangements for extracting light from the devices
    • H10K50/854Arrangements for extracting light from the devices comprising scattering means
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00Nanooptics, e.g. quantum optics or photonic crystals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/85Arrangements for extracting light from the devices
    • H10K50/858Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80Constructional details
    • H10K59/875Arrangements for extracting light from the devices
    • H10K59/877Arrangements for extracting light from the devices comprising scattering means
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80Constructional details
    • H10K59/875Arrangements for extracting light from the devices
    • H10K59/879Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0033Means for improving the coupling-out of light from the light guide
    • G02B6/0035Means for improving the coupling-out of light from the light guide provided on the surface of the light guide or in the bulk of it
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336Illuminating devices
    • G02F1/133602Direct backlight
    • G02F1/133603Direct backlight with LEDs
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301Details of OLEDs
    • H10K2102/331Nanoparticles used in non-emissive layers, e.g. in packaging layer

Definitions

  • OLEDs are the basis for a new display and lighting technology, providing a good match for high resolution or high pixel count high definition display applications, and for efficient, broad area, flexible lighting applications.
  • OLED devices include a thin film of electroluminescent organic material sandwiched between a cathode and an anode, with one or both of these electrodes being a transparent conductor. When a voltage is applied across the device, electrons and holes are injected from their respective electrodes and recombine in the electroluminescent organic material through the intermediate formation of emissive excitons.
  • Efforts have been made to improve the internal quantum efficiency (number of photons generated per electron injected) of OLEDs by means such as modifying the charge injection or transport layers, using fluorescent dyes or phosphorescent materials, or by using multilayer structures (see, for example, K.Meerholz, Adv.Funct.Materials v.11, no.4, p251 (2001 )).
  • Light extraction efficiency (number of photons emerging from the structure vs. the number generated internally) can be influenced by factors external to the emission layers themselves.
  • a bottom emitting OLED may be thought of as consisting of a core containing high index of refraction layers (organic layers for light generation, carrier transport , injection or blocking, and, typically, a transparent conductive oxide layer) and a low index of refraction substrate material (typically glass, but could be a polymer film). Therefore light that is generated within the core may encounter two high index to low index interfaces where it might undergo internal reflection. Light unable to escape the core as a result of encounter at the first interface is confined to a waveguide mode, while light passing through that interface but unable to escape from the substrate as a result of reflection at the substrate-to-air interface is confined to a substrate mode. Similar optical losses occur due to interfaces in top emitting OLEDs.
  • EP 1 830 421 A2 discloses a method to improve light extraction efficiency of a light emitting element such as an electroluminescent element.
  • EP 1 548 856 A2 discloses an organic electroluminescence device with an organic layer.
  • WO 2008/123492 A1 discloses a surface light emitting body with a light transmitting base material and a light scattering layer.
  • WO 02/37580 A1 discloses emissive displays.
  • JP 2006 269163 A , US 2006/0192483 A1 , and JP 2005 353367 A relate to organic electroluminescent elements and devices.
  • V. Kitaev and G. A. Ozin, "Self-Assembled Surface Patterns of Binary Colloidal Crystals", Adv. Mater. 2003, 15, No. 1, January 3, 2003, Wiley-VCH discloses binary colloidal crystal films.
  • a multifunctional optical film for enhancing light extraction includes a flexible substrate, a structured layer, and a backfill layer.
  • the structured layer of extraction elements has a first index of refraction, and a substantial portion of the extraction elements are in optical communication with a light emitting region of a self-emissive light source when the optical film is located against the self-emissive light source.
  • the extraction elements include nanoparticles of different sizes.
  • the backfill layer has a material having a second index of refraction different from the first index of refraction, and the backfill layer forms a planarizing layer over the extraction elements.
  • the multifunctional film product can, in addition to enhancing light extraction, serve additional functions such as a substrate, encapsulant, barrier layer, filter, polarizer, or color converter and may be employed either during or after manufacture of an OLED device.
  • the film construction is based upon photonic crystal structures, or other nanostructures, for improved efficiency of light extraction from the devices by modifying the interface between high and low index layers within the device.
  • Elements of the invention include the provision of structures of dimensions comparable to or less than the wavelength of the light to be controlled, the provision of a material with contrasting index of refraction to fill in the areas surrounding the structures and also to planarize the structure in order to present an essentially smooth surface to come in contact with the OLED structure, and the location of this index-contrasting nanostructured layer within a small enough distance from the light-emitting region to be effective in extracting the light that would otherwise be trapped in that region.
  • TIR total internal reflection
  • the nanostructured index contrast layer be located within the evanescent zone if it is to be most effective in causing extraction of the light from the emission region by scattering or diffraction.
  • the nanostructured index contrast layer need only be in optical communication with a light emitting region of the self-emissive light source when the optical film is located against the self-emissive light source.
  • optical communication means that a significant or substantial portion of the generated optical field from the light source is capable of reaching the scattering particles or nanostructure.
  • Replication master tools can be fabricated with regular or random structures of the required average periodicity for light extraction, 200 nanometers (nm)-2000nm, over increasingly larger areas. Combining this tooling capability with microreplication processes such as continuous cast and cure (3C) enable the formation of the photonic crystal structures, or other nanostructures, on the surface of a film substrate. Examples of a 3C process are described in the following patents: U.S. Patent Nos. 4,374,077 ; 4,576,850 ; 5,175,030 ; 5,271,968 ; 5,558,740 ; and 5,995,690 .
  • Nanostructure refers to structures having at least one dimension (e.g., height, length, width, or diameter) of less than 2 microns and more preferably less than one micron.
  • Nanostructure includes, but is not necessarily limited to, particles and engineered features.
  • the particles and engineered features can have, for example, a regular or irregular shape. Such particles are also referred to as nanoparticles.
  • nanostructured refers to a material or layer having nanostructures.
  • photonic crystal structures refers to periodic or quasi-periodic optical nanostructures interspersed with a material of sufficiently different index of refraction that will enable the structure to produce gaps in the spectrum of allowed electromagnetic modes in the material.
  • index refers to index of refraction
  • backfill refers to the material incorporated into a structure, and of a different index from the structure, to fill in voids in the structure and planarize the structure.
  • extraction elements refers to any type and arrangement of nanostructures enhancing light extraction from self-emissive light sources.
  • the extraction elements are not contained within a volume distribution.
  • FIG. 1 illustrates a structure of bottom emitting OLED device 100 having a light extraction film.
  • a bottom emitting OLED device is defined as an OLED device emitting light through the substrate.
  • Table 1 describes the exemplary elements of device 100 and the arrangement of those elements, as identified by the reference numbers provided in FIG. 1 .
  • Each layer of device 100 can be coated on or otherwise applied to the underlying layer.
  • the substrate 114 is composed of a material, substantially transparent (transmissive) to the desired emitted wavelengths, that provides sufficient mechanical support and thermal stability for the device.
  • Substrate 114 preferably comprises a flexible material. Examples of substrate materials include the following: glass; flexible glass; polyethylene terephthalate ("PET”); polyethylene naphthalate (“PEN”); or other translucent or transparent materials.
  • substrate materials include the following: glass; flexible glass; polyethylene terephthalate (“PET”); polyethylene naphthalate (“PEN”); or other translucent or transparent materials.
  • Substrate 114 can optionally also function as a barrier layer.
  • substrate 114 can optionally contain dyes or particles, and it can be tentered or include prismatic structures.
  • the optional barrier layer 112 effectively blocks or helps prevent permeation of oxygen and water to the layers of the device, particularly the organic layers.
  • barrier layers are described in U.S. Patent Application Publication Nos. 2006/0063015 (describing boron oxide layers with inorganic barrier layers) and 2007/0020451 (describing diamond-like glass (DLG) and diamond-like carbon (DLC)).
  • the electrodes 102 and 106 can be implemented with, for example, transparent conductive oxide (TCO) such as indium tin oxide (ITO) or metals with the appropriate work function to make injection of charge carriers such as calcium, aluminum, gold, or silver.
  • TCO transparent conductive oxide
  • ITO indium tin oxide
  • metals with the appropriate work function to make injection of charge carriers such as calcium, aluminum, gold, or silver.
  • the organic layers 104 can be implemented with any organic electroluminescent material such as a light-emitting polymer, an example of which is described in U.S. Patent No. 6,605,483 .
  • suitable light emitting materials include evaporated small molecule materials, light-emitting dendrimers, molecularly doped polymers, and light-emitting electrochemical cells.
  • the light extraction film 116 in this embodiment is composed of substrate 114, optional barrier layer 112, low index structure 110, and high index structure 108.
  • the high index structure uses a backfill medium to effectively provide a planarizing layer over the low index structure in order to make the light extraction film sufficiently planar to allow OLED fabrication.
  • the backfill layer can alternatively have other optical properties.
  • the backfill layer material can function as a barrier to moisture and oxygen or provide electrical conduction, possibly in addition to having barrier properties, depending upon the type of material used.
  • the backfill layer can alternatively be implemented with an optically clear adhesive, in which case the extraction film can be applied to top emitting OLED device, for example.
  • a stabilization layer can optionally be coated on the device before applying the backfill layer.
  • the low index structure 110 has a material with an index substantially matched to the underlying layer, typically the substrate.
  • the low index structure 110 is composed of a nanostructured layer, which can have a periodic, quasi-periodic, or random distribution or pattern of optical nanostructures, including photonic crystal structures. It includes discrete nanoparticles.
  • the nanoparticles can be composed of organic materials or other materials, and they can have any particle shape.
  • the nanoparticles can alternatively be implemented with porous particles.
  • the distribution of nanostructures can also have varying pitches and feature size. At least a portion of the extraction elements or nanostructures are preferably in contact with the flexible substrate, and the extraction elements may have voids beneath them.
  • the layer of nanoparticles can be implemented with nanoparticles in a monolayer, with a layer having agglomerations of nanoparticles, or in a multi-layer.
  • the addition of small SiO 2 nanoparticles to suspensions of larger SiO 2 nanoparticles for low index structure 110 can significantly improve the uniformity of the larger nanoparticles in coatings made from the suspension.
  • low index structure 110 can include the additional of 5nm diameter SiO 2 nanoparticles in coatings made from suspensions of 440nm diameter SiO 2 nanoparticles.
  • These small and large nanoparticles can be surface treated or non-treated.
  • the large nanoparticles can comprises two or more different sizes of large nanoparticles.
  • the large nanoparticles have diameters in the range of 60nm to 10 microns, preferably 100nm to 1 micron, or more preferably 100nm to 500nm.
  • the small nanoparticles have diameters in the range of 3nm to 50nm.
  • the nanoparticles can comprise one or more of the following: metal oxide particles; organic polymer particles; metal particles; or composite particles.
  • the backfill layer has a lower index than the structured layer, then the backfill layer preferably has a thickness substantially equal to the extraction elements.
  • the backfill layer has a higher index than the structured layer, then the backfill layer can be thicker than the extraction elements provided it can still interact with the evanescent wave.
  • the structured layer and backfill layer are preferably in sufficient proximity to the light output surface in order to at least partially effect the extraction of light from that surface.
  • the nanostructured features in layer 110 can be fabricated using any printing techniques for replication of submicron features such as the following: imprinting; embossing; nanoimprinting; thermal- or photo-nanoimprint lithography; injection molding; or nanotransfer printing. Another technique for fabricating the extraction elements is described in Example 18 in U.S. Patent No. 6,217,984 .
  • the high index structure 108 is a high index material providing index contrast to the adjacent low index nanostructured layer and provides an effective planarization layer to it.
  • the index of refraction mismatch between nanostructured layer 110 and backfill medium 108 at the emission wavelength(s) is referred to as ⁇ n, and a greater value of ⁇ n generally provides better light extraction.
  • the value of ⁇ n is greater than or equal to 0.3, preferably greater than or equal to 0.4, 0.5, or 1.0. Any index mismatch between the extraction elements and backfill medium will provide for light extraction; however, a greater mismatch tends to provide greater light extraction and is thus preferred.
  • suitable materials for backfill medium 108 include the following: high index inorganic materials; high index organic materials; a nanoparticle filled polymer material; silicon nitride; polymers filled with high index inorganic materials; and high index conjugated polymers.
  • high index polymers and monomers are described in C.Yang, et al., Chem.Mater. 7, 1276 (1995 ), and R.Burzynski, et al., Polymer 31, 627 (1990 ) and U.S. Patent No. 6,005,137 .
  • polymers filled with high index inorganic materials are described in U.S. Patent No. 6,329,058 .
  • the backfill layer can be applied to form the planarizing layer using, for example, one of the following methods: liquid coating; vapor coating; powder coating; or lamination.
  • Functionality can be added to the construction by depositing on it a transparent conductor such as ITO (n ⁇ 1.9-2.1) with high index, high transparency and low sheet resistivity, to serve as the anode for the OLED device.
  • a transparent conductor such as ITO (n ⁇ 1.9-2.1) with high index, high transparency and low sheet resistivity
  • the ITO can even be used as the backfill for the structure, if the layer can fill the structures and form into a smooth layer without adverse effects on the optical or electrical properties.
  • alternating metallic and organic layers may be deposited to form a transparent conductive overlayer (on the backfill layer) in the manner as described in U.S. Patent Application Publication No. 2004/0033369 .
  • photonic quasicrystal structures are designed using tiling rules; they have neither true periodicity nor translation symmetry but have a quasi-periodicity with long-range order and orientation symmetry, examples of which are described in the following reference: B. Zhang et al., "Effects of the Artificial Ga-Nitride/Air Periodic Nanostructures on Current Injected GaN-Based Light Emitters," Phys.Stat.Sol.(c) 2(7), 2858-61 (2005 ).
  • the photonic quasicrystal structures offer the possibility of a pseudogap for all propagation directions, and they exhibit unique light scattering behaviors.
  • these patterns of quasiphotonic crystal structures can eliminate artifacts resulting from the regularity of conventional photonic crystal structures, and they can be used to tailor unique light emission profiles and possibly can eliminate undesirable chromatic effects when working with broadband OLED emitters.
  • Photonic crystal structures are described in the following patents: U.S. Patent Nos. 6,640,034 ; 6,901,194 ; 6,778,746 ; 6,888,994 ; 6,775,448 ; and 6,959,127 .
  • Embodiments can involve the incorporation of the diffractive or scattering nanostructures into a film product which could be continuously produced, for example, on a web line having a polymer film or ultrabarrier coated film substrate fed to a 3C replication process followed by deposition of a high index backfill medium.
  • Alternate ways to incorporate the diffractive or scattering nanoparticles into the film include solution coating a dispersion of particles. This film can be designed to be used directly as the substrate on which a bottom emitting OLED is fabricated, enabling the production of a film capable of many uses in addition to enhancing light extraction.
  • Ultrabarrier films include multilayer films made, for example, by vacuum deposition of two inorganic dielectric materials sequentially in a multitude of layers on a glass or other suitable substrate, or alternating layers of inorganic materials and organic polymers, as described in U.S. Patent Nos. 5,440,446 ; 5,877,895 ; and 6,010,751 .
  • surface coatings or structures can be applied to the air surface of the light extraction film in order to further increase the functionality and possibly value of a light extraction film.
  • Such surface coatings can have, for example, optical, mechanical, chemical, or electrical functions.
  • coatings or structures include those having the following functions or properties: antifog; antistatic; antiglare; antireflection; antiabrasion (scratch resistance); antismudge; hydrophobic; hydrophilic; adhesion promotion; refractive elements; color filtering; ultraviolet (UV) filtering; spectral filtering; color shifting; color modification; polarization modification (linear or circular); light redirection; diffusion; or optical rotation.
  • Other possible layers to be applied to the air surface include a barrier layer or a transparent electrically conductive material.
  • FIG. 2 illustrates a structure of top emitting OLED device 120 with a film substrate having a light extraction film.
  • Table 2 describes the exemplary elements of the device 120 and the arrangement of those elements, as identified by the reference numbers provided in FIG. 2 . Each layer of the device can be coated on or otherwise applied to the underlying layer. The configurations shown in FIGS. 1 and 2 are provided for illustrative purposes only, and other configurations of bottom emitting and top emitting OLED display devices are possible.
  • the light extraction film 142 in this embodiment is composed of substrate 122, optional barrier layer 124, low index structure 126, and high index structure 128.
  • Low index structure 126 and high index structure 128 can be implemented with the exemplary materials and constructions described above.
  • Layers 128 and 130 can optionally be implemented with a single layer.
  • the substrates 122 and 140, optional barrier layer 124, electrodes 132 and 138, and organic layers 136 can be implemented with the exemplary materials identified above.
  • Substrate 140 can also be optionally implemented with an opaque material such as a metal foil.
  • Optional thin film encapsulant 134 can be implemented with, for example, any suitable material for protecting the organic layers from moisture and oxygen. Examples of encapsulants for OLED devices are described in U.S. Patent No. 5,952,778 and U.S. Patent Application Serial No. 11/424997, filed June 19, 2006 .
  • OLED devices especially top emitting OLED devices as shown in FIG. 2
  • a thin film encapsulant typically on a semitransparent electrode.
  • This construction of an OLED device provides an advantage; in particular it creates access to the critical high index device-air interface after the completion of device fabrication, enabling a lamination process for the application of the light extraction film.
  • embodiments include a light extraction film as described above for bottom emitting OLED devices.
  • the film can be designed to be the capping layer on a top emitting OLED structure when combined with a suitable high index adhesive to serve as the optical layer 130 in order to optically couple the OLED device to the light-extracting layer.
  • the encapsulant material may itself serve as the index contrast material which backfills the nanostructures to form the light extraction layer.
  • Top emitting OLED device 120 or bottom emitting OLED device 100 can also be used to implement an OLED solid state lighting or display element.
  • substrates useful in top emitting OLED solid state lighting devices including flexible metal foils, are described in the following papers: D.U. Jin et al., "5.6-inch Flexible Full Color Top Emission AMOLED Display on Stainless Steel Foil," SID 06 DIGEST, pp. 1855-1857 (2006 ); and A. Chwang et al., "Full Color 100 dpi AMOLED Displays on Flexible Stainless Steel Substrates," SID 06 DIGEST, pp. 1858-1861 (2006 ).
  • FIG. 3 is a diagram illustrating a device 220 having spatially modulated OLED devices for use in solid state lighting devices.
  • Device 220 includes a substrate 222 supporting a plurality of OLED devices 223, 224, 225, and 226, each of which may correspond with the structures described above with respect to bottom or top emitting OLED display devices.
  • Each of the OLED devices 223-226 can be individually controlled as represented by lines 228 and 230, which would provide electrical connections to the anodes and cathodes in devices 223-226.
  • Device 220 can include any number of OLED devices 223-226 with electrical connections, and substrate 222 can be scaled to accommodate them.
  • the individual control of devices 223-226, via connections 228 and 230, can provide for spatial modulation of them such that they are individually or in groups lighted in a particular sequence or pattern.
  • Device 220 can be used in solid state light, for example, on a rigid or flexible substrate 222.
  • FIG. 4 is a diagram of a top emitting OLED backlight unit 180 with light extraction film.
  • Table 3 describes the exemplary elements of the backlight unit 180 and the arrangement of those elements, as identified by the reference numbers provided in FIG. 4 .
  • Each layer of backlight unit 180 can be coated on or otherwise applied to the underlying layer.
  • bottom emitting OLEDs can also be used for backlight units.
  • the light extraction film 208 in this embodiment is composed of low index structure 190 and high index structure 192.
  • the light extraction film can optionally also include prism layer 184 and diffuser 188.
  • Low index structure 190 and high index structure 192 can be implemented with the exemplary materials and constructions described above.
  • the other elements of this embodiment, as provided in Table 3, can be implemented with the exemplary materials identified above.
  • Layers 192 and 194 can alternatively be implemented with a single layer.
  • FIG. 5 is a diagram illustrating OLED devices used as a liquid crystal display (LCD) backlight unit 242 for an LCD panel 240.
  • Backlight unit 242 may correspond with the structure 180.
  • the backlight unit 242 can alternatively be implemented with the spatially modulated light panel shown in FIG. 3 .
  • LCD panel 240 typically includes the entire LCD device except the backlight and drive electronics.
  • LCD panel 240 typically includes the backplane (subpixel electrodes), front and back plates, liquid crystal layer, color filter layer, polarizing filters, and possibly other types of films.
  • Use of OLED devices as a backlight may provide for a thin, low power backlight for LCDs.
  • An example of LCD panel components and a backlight unit are described in U.S. Patent No. 6,857,759 .
  • FIGS. 6-9 are diagrams depicting the possible spatial configurations of extraction elements.
  • FIG. 6 illustrates a low index structure 250, having a regular pattern of nanostructures, with a high index structure 251 providing a planarizing layer over the nanostructures.
  • the structures 250 and 251 are located between a low index substrate 246 and an OLED device region 247.
  • FIG. 7 illustrates a low index structure 252, having an irregular pattern of nanostructures, with a high index structure 253 providing a planarizing layer over the nanostructures.
  • the structures 252 and 253 are located between a low index substrate 248 and an OLED device region 249.
  • the low and high index structures are located between a substrate and an OLED device (light emitting) region.
  • FIG. 8 illustrates high index extraction elements 255 within a low index backfill region 254 with the low index region 254 providing the planarizing layer.
  • the extraction elements 255 and backfill 254 are located between a low index substrate 260 and an OLED device region 259.
  • FIG. 9 illustrates low index extraction elements 257 within a high index backfill region 256 with the high index region 256 providing the planarizing layer.
  • the extraction elements 257 and backfill 256 are located between a low index substrate 261 and an OLED device region 262.
  • the extraction elements are concentrated in the evanescent zone.
  • the layers shown in FIGS. 6-9 illustrate patterns and interfaces of the low index and high index structures described above.
  • FIGS. 10-14 are top view diagrams depicting possible surface configurations of extraction elements.
  • FIGS. 10 and 11 illustrate regular periodic arrays of extraction elements.
  • FIG. 12 illustrates a random distribution of extraction elements.
  • FIG. 13 illustrates patterned regions of extraction elements.
  • FIG. 13 illustrates portions of features, possibly in a regular pattern 264 or an irregular pattern 265, interspersed within a different distribution of features 263.
  • the regular or irregular patterns 264 and 265, respectively, along with the different distribution 263 may each have periodic, quasi-periodic, or random distributions of extraction elements.
  • Such regions of patterns may be useful to optimize extraction of particular wavelengths of light at those regions, for example wavelengths corresponding with red, green, and blue light.
  • the extraction regions can correspond and be aligned the red, green, and blue regions comprising pixels of a display device, and each extraction region can each be optimized to extract light from the corresponding red, green, and blue regions.
  • FIG. 14 illustrates quasicrystal (tiled patterns) of extraction elements.
  • FIGS. 10-14 illustrate possible surface configurations of the nanostructures or other extraction elements described above with a backfill medium providing the planarizing layer over the nanostructures.
  • Additional techniques could include using lithography or interference lithography to expose nanoscale regions in a photosensitive polymer deposited on a flexible polymer web. After the exposure and development steps, the remaining photosensitive polymer would then define a nanostructured surface. Alternatively, this nanostructured photosensitive polymer surface can serve as an etch mask for exposure of the surface in an etching process. This etching technique would transfer the nanoscale pattern into the surface of the underlying polymer web or into a layer of a harder material, such as a silicon oxide, which had been deposited on the polymer web prior to the lithographic steps. The nanoscale surface defined in any of these manners could then be backfilled with an index contrasting medium to form the light scattering or diffracting layer.
  • This embodiment provides enhanced light extraction from an OLED using an index-contrasting film with randomly distributed high index nanostructures created by coating nanoparticles such as, for example, ITO, silicon nitride (Si 3 N 4 , referred to here as SiN), CaO, Sb 2 O 3 , ATO, TiO 2 , ZrO 2 , Ta 2 O 5 , HfO 2 , Nb 2 O 3 , MgO, ZnO, In 2 O 3 , Sn 2 O 3 , AlN, GaN, TiN, or any other high index materials on a substrate used in OLED fabrication or encapsulation, and then applying a low index coating, such as SiO 2 , Al 2 O 3 , DLG, DLC, or polymeric materials over the nanoparticles to provide the index contrast needed for scattering or diffraction efficiency and to planarize the surface.
  • nanoparticles such as, for example, ITO, silicon nitride (Si 3 N 4 , referred to here as SiN),
  • the randomly distributed nanostructures can be in contact with the substrate, proximate the substrate, grouped together in places, or in any random configuration proximate the substrate.
  • a converse construction, potentially providing similar effectiveness, can comprise a random distribution of low index nanoparticles or nanostructures such as SiO 2 , porous SiO 2 , Borosilicate (BK), Al 2 O 3 , MgF 2 , CaF, LiF, DLG, DLC, metal particles such as silver or gold particles, poly(methyl methacrylate) (PMMA), polycarbonate, PET, low index polymers, or any other low index materials with a contrasting high index filler material such as vapor deposited Si 3 N 4 or a solvent-coated particle-filled polymer or a high index polymer.
  • the substrate can optionally have one or more of the following coatings: an antistatic coating; or an adhesion promotion coating.
  • Coating processes such as dip coating, knife coating, dye coating, and roll-to-roll coating may be used for distributing the nanoparticles on the surface, and a similar process may be used to coat the backfill/planarization layer.
  • the use of such techniques should render the process simple, easily scaled for manufacturing, and suitable for incorporation in film products manufactured via web line or roll-to-roll processes.
  • the roll-to-roll continuous process fabrication of light extraction films can include assembling monolayer or sub-monolayer coatings of low index nanoparticles on a plastic substrate, the applying an overcoat of high index material.
  • An example of such a roll-to-roll process includes coating bare functionalized silica nanoparticles on plastic (PET) substrates and then overcoating those nanoparticles with a high index backfill material.
  • the high index backfill materials can be obtained by loading epoxy or acrylate polymers with high index nanoparticles such as ZrO 2 or TiO 2 . Additional high index materials are described in U.S. Patent Application Serial No. 12/262393, filed October 31, 2008 .
  • One particular manufacturing method involves applying nanoparticles having a first index of refraction onto a flexible substrate and overcoating a backfill layer on the nanoparticles to form a planarizing layer over them.
  • the backfill layer comprises a material having a second index of refraction different from the first index of refraction.
  • a substantial portion of the nanoparticles are within an evanescent zone adjacent to a light emitting region of a self-emissive light source when the optical film is located against the self-emissive light source.
  • a substantial portion of the nanoparticles can be in contact with the substrate to be within the evanescent zone, although in some embodiments the substantial portion of the nanoparticles in the evanescent zone need not be in contact with the substrate.
  • Applying the nanoparticles can involve coating the nanoparticles dispersed in a solvent onto the flexible substrate and allowing the solvent to evaporate before overcoating the backfill layer. Applying the nanoparticles can also involve applying them in dry form to the flexible substrate and then overcoating them with the backfill layer.
  • An alternative to the method involves using substrate with a release agent, in which the particles are applied to a substrate with a release agent, the substrate with the particles is applied to a device substrate with the particles in contact with it, and then the substrate is released to transfer the particles to the device substrate.
  • On particular method involves a single process to coat the substrate with nanoparticles, dry it, coat the backfill layer, dry it again, and then cure the resulting film.
  • Yet another particular method involves a first process to coat the substrate with nanoparticles, dry it, and wind up the coating film, and then a second process to unwind the film, coat the backfill layer, dry it again, and then cure the resulting film.
  • One solution for forming a master tool having nanostructures involves the use of interference lithography. Regular periodic features as small as 100nm-150nm can be quickly written using this method. An advantage involves being able to write these patterns over larger areas, which can make the process more amenable to manufacturing.
  • Production of a master tool for replication of the pattern can involve the following.
  • a substrate is coated with an overlayer of photoresist and then illuminated with one or more UV interference patterns to expose the resist in a regular pattern with the desired feature sizes.
  • Development of the resist then leaves an array of holes or posts.
  • This pattern can subsequently be transferred into the underlying substrate through an etching process.
  • a metal tool can be made using standard electroforming processes. This metal replica would then become the master tool.
  • a solution is prepared comprising nanoparticles of the appropriate size and with the appropriate surface modifications to prevent agglomeration.
  • Methods for preparing such solutions are generally specific to the particular nanoparticles to be dispersed; general methods have been described elsewhere, including U.S. Patent No. 6,936,100 and Molecular Crystals and Liquid Crystals, 444 (2006) 247-255 .
  • the solution is then coated onto a flexible substrate using one of a variety of solvent coating techniques, including knife coating, dip coating, spray coating, dye coating, or roll-to-roll coating. Pretreatment of the substrate using methods such as plasma etching may be required in order to assure uniformity of the solution coating.
  • the nanoparticles should be distributed in a way that is microscopically random but macroscopically uniform. As was the case with the uniform tool fabrication process described above, this pattern could then be transferred to an underlying substrate material through an etching or embossing process, or a metal tool can be made using standard electroforming processes.
  • a flat master tool may then be tiled together to form a larger tool, as described in U.S. Patent No. 6,322,652 , or may be formed into a cylindrical tool for compatibility with a roll-to-roll replication process.
  • replication of the structure into a polymer can be done using one of a variety of replication processes, including the 3C process.
  • the substrate for this replication could be any polymer sheeting compatible with the chosen replication process; it may be already coated with the ultrabarrier film as described above.
  • Backfilling would then be performed downstream in, for example, a chemical vapor deposition (CVD) or sputtering process which can deposit a high index material, such as SiN or ITO, which is capable of filling the structures and then leveling out into a smooth layer. If SiN is used, this might then be followed by an ITO deposition process if a conductive upper layer is required.
  • the downstream backfilling may be performed in a solvent coating process using suitable materials.
  • Example 1 190 nm SiO 2 Nanoparticles with No 5 nm SiO 2 Nanoparticles (Comparative Example)
  • Dispersions of spherical silica nanoparticles with nominal diameter of 190 nm were obtained from the Nissan Chemical, 10777 Westheimer, Suite 830, Houston, TX 77042, U.S.A.
  • the nanoparticles were treated with polyethylene oxide (PEO and dialyzed, 142971-86-4, 190 nm silica with PEO covered and dialyzed, 33.6% solids).
  • the process details of treated 190 nm SiO 2 nanoparticles with PEO are as follows. 363 grams of Nissian MP-4540 (100 grams of silica) was added to a reaction vessel along with 7.5 grams of A1230 polyethylene oxide silane from Momentive Performance Chemicals. The mixture was reacted for 16 hours at 80°C. The reaction mixture was then dialyzed to remove any unreacted silane and other impurities. The solution was place in a 2 Spectra/Por Dialysis membrane having a MWCO (Molecular Weight Cut-Off) of 12-14,000. The material was dialyzed for 24 hours against constantly flowing tap water.
  • the resulting nanoparticle suspension was diluted in 1 methoxy 2 propanol to produce suspensions having 2 percent by weight solids content.
  • the 190 nm SiO 2 nanoparticle solution was coated on a PET substrate by a dip coating (coating speed: 65mm/min). It was shown from SEM images that there was a de-wetting issue resulting in regions of the substrate having no particle coating.
  • Example 2 Improved Coating of 190 nm SiO 2 Nanoparticles Via Addition of 5 nm SiO 2 Nanoparticles (Treated)
  • a 2wt% suspension of 190 nm SiO 2 nanoparticles was prepared as described in Example 1, but with the addition of 1.1 wt% of 5 nm SiO 2 (treated by PEO: 147426-45-01,5 nm silica particles treated with Silquest A1230).
  • the 190 nm SiO 2 nanoparticles were coated on a PET substrate by a dip coating (coating speed of 65 mm/min as in Example 1). Through comparison of SEM images from Example 1 and this sample, the uniformity of the coating was shown to have been improved by adding the small nanoparticles, although the de-wetting of the nanoparticles coating had not completely disappeared.
  • Example 3 Improved Coatings of 190 nm SiO 2 Nanoparticles Via Addition of Unmodified 5 nm SiO 2 Nanoparticles
  • a 2 wt% of 190 nm SiO 2 nanoparticles was prepared as described as in Example 1, but with the addition of 1.1 wt% of 5 nm SiO 2 (unmodified small 5 nm SiO 2 nanoparticles from Nalco Company, Nalco 2326). It was clearly shown from SEM images that unmodified small SiO 2 nanoparticles can significantly improve the large nanoparticle coating uniformity.
  • Example 4 190nm SiO 2 Nanoparticles with 5 nm Modified SiO 2 Nanoparticles (Modified with Isooctyltrimethoxysilane and Methyltrimethoxysilane)
  • a 2wt % of 190 nm SiO 2 nanoparticles was prepared as described as in Example 1, but with the addition of 1.1 wt% of 5 nm SiO 2 nanoparticles modified with isooctyltrimethoxysilane and methytrimethoxysilane.
  • the 5 nm nanoparticle powder was first dissolved in isopropanol to produce suspensions having 10 percent by weight solids content). As was shown through SEM images, the coating uniformity was improved, although the de-wet of the nanoparticles coating had not completely disappeared.
  • Example 5a 440 nm SiO 2 Nanoparticles Coated by Roll-to-Roll Process without Small Nanoparticles (Comparative Example for Example 5b)
  • Dispersions of spherical silica nanoparticles with nominal diameter of 440 nm were obtained from the Nissan Chemical (Houston Office (Chemical Business), 10777 Westheimer, Suite 830, Houston, TX 77042, U.S.A..
  • the nanoparticle solution was diluted in 1 methoxy 2 propanol to produce a suspension having 5 percent by weight solids content.
  • the 440 nm SiO 2 nanoparticles were coated on a corona-treated PET film (6-8mil thickness) by roll-to roll-process using a 5 mil coating gap (web speed of 10 fpm, ind. pump speed of 1.2 cc/min). The resulting coating was first dried in air at room temperature, then subsequently further dried at 180°F.
  • Example 5b 440nm SiO 2 Nanoparticles Coated by Roll-to-Roll Process with Small Nanoparticles
  • Example 5a 2.5 wt% of 440 nm SiO 2 nanoparticles were prepared as in Example 5a, but then 1 wt% of modified 5 nm SiO 2 nanoparticles, prepared as in the Example 2, was added.
  • the 440 nm SiO 2 nanoparticles were coated on the corona-treated PET film using the same conditions as in Example 5a.
  • silica nanoparticles of 93 nm nominal diameter obtained from the Nalco company
  • dodecylbenzenesulfonic sodium salt (DS-10) surfactant obtained from Aldrich. Using these materials with different coating conditions, close-packed monolayers of nanoparticles, or sparse discontinuous layers, could be achieved.
  • a silica nanoparticle dispersion produced by diluting a 2 wt% nanoparticles dispersion in H 2 O to 1 wt% nanoparticles with DS-10 was coated on a corona-treated PET film (6-8 mil thickness) by the roll-to-roll process using a 5 mil gap (web speed of 10 fpm, dispersion delivery rate of 3 cc/min). The coating was dried in air at room temperature, and then subsequently it was further dried at 180°F. It was shown through a SEM photo of the resulting nanoparticle that a uniform and close-packed monolayer of silica nanoparticles was produced.
  • Silica nanoparticle dispersion as above was coated on corona-treated PET film (6-8 mil thickness) by the roll-to-roll process with a 5 mil gap and lower dispersion delivery rate (web speed of 10 fpm, dispersion delivery rate of 1.5 cc/min). The resulting coating was dried in air at room temperature, and subsequently further dried at 180°F on the web.
  • Si 3 N 4 layer was applied over the silica nanoparticle coating using plasma-enhanced chemical vapor deposition (PECVD, Model PlasmaLab System100 available form Oxford Instruments, Yatton, UK). Conditions used in the Si 3 N 4 deposition are shown in Table 4. Table 4 - Conditions Used for Depositing S3iN4 Layer Reactant/Condition Value SiH 4 400 sccm NH 3 20 sccm N 2 600 sccm Pressure 650 mTorr Temperature 60°C High frequency (HF) power 20 W Low frequency (LF) power 20 W
  • the refractive index of the Si 3 N 4 overcoating was measured using a Metricon Model 2010 Prism Coupler and was found to be 1.7. At the completion of the PECVD process, a low index scattering center with high index backfilling film had been generated.
  • ITO indium gallium
  • a simple green organic emitting layer and cathode were deposited to complete the OLED.
  • the OLEDs were fabricated by standard thermal deposition in a bell-jar vacuum system.
  • the OLED layers were deposited through a 40 mm x 40 mm shadow mask covering the 5 mm x 5 mm ITO pixels in the following order: TNATA:FeCl3 (3000A, 5% FeCl3)/NPD(400A)/Alq:C545T(300A, 2%)/Alq(200A)/7ALiF/Al.
  • the 5 mm x 5 mm shadow mask was then realigned, and 250 nm of Al metal was deposited to form the cathodes contacting the tops of the pixels.
  • This process provided OLED devices containing several independently addressable 5 mm x 5 mm pixels with 4 pixels disposed over nanoparticles.
  • Electroluminescence measurements showed enhanced OLED light extraction from the nanoparticle coated pixels. An improvement of 50% at current densities between 2-20 mA/cm 2 was shown with this modification.
  • Example 7 Light Extracting OLED Substrate having Nanoparticles Overcoated by High Index Polymer Applied in Roll-to-Roll Process.
  • the target thickness of the high index polymer was 300 nm; SEM images indicated an actual thickness of about 300 nm in excellent agreement with the target thickness.
  • the surface of the roll-to-roll coating was shown to be very smooth compared with Si 3 N 4 deposited by plasma enhanced chemical vapor deposition.
  • Example 8 93nm SiO2 nanoparticles coated by roll-to-roll process with 60nm SiN overcoated on NPs as a stabilization layer
  • Dispersions of 93nm silica nanoparticles were obtained from the Nalco company.
  • Polyvinyl alcohol (PVA, 98 mole % hydrolyzed, MW 78000) was obtained from Polysciences, Inc., and was dissolved in water with 1wt % solid content for the related experiments.
  • Dodecylbenzenesulfonic sodium salt (DS-10) surfactant was obtained from Alderich.
  • a silica nanoparticle (NP) dispersion solution (93nm, 1wt%, 0.1-lwt% DS-10) was coated on PET film (6-8mil thickness) by a roll-to-roll process using a 5 mil gap (web speed of 10 fpm, dispersion delivery rate of 3 cc/min). The coating was dried in air at room temperature, and then subsequently it was further dried at 180°F.
  • the silica-nanoparticle-coated film was then over-coated with a 60nm thick layer of silicon nitride by plasma-enhanced chemical vapor deposition (PECVD), for stabilization of the NPs (PECVD, Model PlasmaLabTM System100 available form Oxford Instruments, Yatton, UK).
  • PECVD plasma-enhanced chemical vapor deposition
  • the parameters used in the PECVD process are described in Table 5.
  • the refractive index of the SiN core layer was measured using a Metricon Model 2010 Prism Coupler, and was found to be 1.7.
  • Light-Hammer 6 UV (Gaithersburg, Maryland) processor equipped with an H-bulb, operating under nitrogen atmosphere at 100% lamp power at a line speed of 30 feet/min (2 pass).
  • the thickness of the high-index coating was measured to be approximately 150-200 nm.
  • the refractive index of the high index coating is measured as 1.85 using Metricon Prism Coupler.
  • the OLEDs were fabricated by standard thermal deposition in a vacuum system at base pressure of ca. 10 -6 Torr. The following OLED construction was deposited: HIL(300nm)/HTL(40nm)/EML(30nm,6%)/Alq(20nm)/ LiF(1nm)/Al(200nm). After completion, the OLED was encapsulated with 3M encapsulation barrier film employing SAES getter as a desiccant and oxygen scavenger in between the encapsulation film and the OLED cathode.
  • the 5mm x 5mm shadow mask was then realigned, and 200nm of Al metal was deposited to form the cathodes contacting the tops of the pixels.
  • This process provided OLED devices containing several independently addressable 5mm x 5mm pixels with 4 pixels disposed over nanoparticles.
  • Electroluminescence measurements showed enhanced OLED light extraction from the nanoparticle coated pixels. An improvement of 50-100% was shown with this modification.

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Description

    BACKGROUND
  • Organic Light Emitting Diodes (OLEDs) are the basis for a new display and lighting technology, providing a good match for high resolution or high pixel count high definition display applications, and for efficient, broad area, flexible lighting applications. OLED devices include a thin film of electroluminescent organic material sandwiched between a cathode and an anode, with one or both of these electrodes being a transparent conductor. When a voltage is applied across the device, electrons and holes are injected from their respective electrodes and recombine in the electroluminescent organic material through the intermediate formation of emissive excitons.
  • In OLED devices, over 70% of the generated light is typically lost due to processes within the device structure. The trapping of light at the interfaces between the higher index organic and Indium Tin Oxide (ITO) layers and the lower index substrate layers is the major cause of this poor extraction efficiency. Only a relatively small amount of the emitted light emerges through the transparent electrode as "useful" light. The majority of the light undergoes internal reflections, which result in its being emitted from the edge of the device or trapped within the device and eventually being lost to absorption within the device after making repeated passes.
  • Efforts have been made to improve the internal quantum efficiency (number of photons generated per electron injected) of OLEDs by means such as modifying the charge injection or transport layers, using fluorescent dyes or phosphorescent materials, or by using multilayer structures (see, for example, K.Meerholz, Adv.Funct.Materials v.11, no.4, p251 (2001)). Light extraction efficiency (number of photons emerging from the structure vs. the number generated internally) can be influenced by factors external to the emission layers themselves.
  • A bottom emitting OLED may be thought of as consisting of a core containing high index of refraction layers (organic layers for light generation, carrier transport , injection or blocking, and, typically, a transparent conductive oxide layer) and a low index of refraction substrate material (typically glass, but could be a polymer film). Therefore light that is generated within the core may encounter two high index to low index interfaces where it might undergo internal reflection. Light unable to escape the core as a result of encounter at the first interface is confined to a waveguide mode, while light passing through that interface but unable to escape from the substrate as a result of reflection at the substrate-to-air interface is confined to a substrate mode. Similar optical losses occur due to interfaces in top emitting OLEDs.
  • Various solutions have been proposed to affect light reaching the substrate-to-air interface by disturbing that interface (e.g., microlenses or roughened surfaces). Others have introduced scattering elements into the substrate or into an adhesive (see Published PCT Application No. WO2002037580A1 (Chou )), thereby interrupting the substrate modes to redirect that light out of the device. There have even been some preliminary attempts to disturb the core-to-substrate interface by introducing scattering or diffractive elements at this interface. Detailed analysis has shown that scattering or diffracting structures will be most effective in extraction light when located at this interface (M.Fujita, et al.; Jpn.J.Appl.Phys. 44 (6A), pp.3669-77 (2005)). Scattering efficiency is maximized when the index contrast between the scattering or diffractive elements and the backfill material is large and when the length scale of the index contrast variations is comparable to the wavelength of the light (see, for example, F.J.P.Schuurmans, et al.; Science 284 (5411), pp.141-143 (1999)).
  • Fabrication of defect-free OLED devices in contact with this light extracting layer will require a smooth planar surface, so planarity of the top surface of a light extraction film is important. There has been, however, some work on corrugating the electrode structure in order to couple light out of the OLED (M.Fujita, et al.; Jpn.J.Appl.Phys. 44 (6A), pp.3669-77 (2005)); the resultant effects on the electric fields in the device are expected to have deleterious effects. So great care must be taken to not adversely affect the electrical operation of the device while disturbing this interface. Practical solutions to balancing these conflicting issues have not yet been proposed.
  • Similar problems in external efficiency exist with inorganic light-emitting diodes (LEDs), where the very high refractive indices of the active materials can severely limit the extraction of internally generated light. In these cases, there have been some attempts to utilize photonic crystal (PC) materials to improve the extraction efficiency (S.Fan, Phys.Rev.Letters v.78, no.17, p.3294 (1997); H.Ichikawa, Appl.Phys.Letters V.84, p.457 (2004)). Similar reports on the use of PCs in connection with OLED efficiency improvement have begun to appear (M.Fujita, Appl.Phys.Letters v.85, p.5769 (2004); Y.Lee, Appl.Phys.Letters v.82, p.3779 (2003)), but previously reported results have involved time-consuming and costly procedures which do not lend themselves incorporation into existing OLED fabrication processes.
  • Accordingly, a need exists for a product which can enhance light extraction from OLED devices in a form which is compatible with fabrication processes for these devices.
  • EP 1 830 421 A2 discloses a method to improve light extraction efficiency of a light emitting element such as an electroluminescent element. EP 1 548 856 A2 discloses an organic electroluminescence device with an organic layer. WO 2008/123492 A1 discloses a surface light emitting body with a light transmitting base material and a light scattering layer. WO 02/37580 A1 discloses emissive displays. JP 2006 269163 A , US 2006/0192483 A1 , and JP 2005 353367 A relate to organic electroluminescent elements and devices. V. Kitaev and G. A. Ozin, "Self-Assembled Surface Patterns of Binary Colloidal Crystals", Adv. Mater. 2003, 15, No. 1, January 3, 2003, Wiley-VCH discloses binary colloidal crystal films.
  • SUMMARY
  • According to the invention, a multifunctional optical film as recited in independent claim 1 is provided. The dependent claims define embodiments.
  • A multifunctional optical film for enhancing light extraction, consistent with the present invention, includes a flexible substrate, a structured layer, and a backfill layer. The structured layer of extraction elements has a first index of refraction, and a substantial portion of the extraction elements are in optical communication with a light emitting region of a self-emissive light source when the optical film is located against the self-emissive light source. The extraction elements include nanoparticles of different sizes. The backfill layer has a material having a second index of refraction different from the first index of refraction, and the backfill layer forms a planarizing layer over the extraction elements.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • The accompanying drawings are incorporated in and constitute a part of this specification and, together with the description, explain the advantages and principles of the invention. In the drawings,
    • FIG. 1 is a diagram of a bottom emitting OLED display device with a light extraction film;
    • FIG. 2 is a diagram of a top emitting OLED display device with a light extraction film;
    • FIG. 3 is a diagram illustrating spatially modulated OLEDs for a solid state lighting element;
    • FIG. 4 is a diagram of an OLED backlight unit with a light extraction film;
    • FIG. 5 is a diagram illustrating OLEDs used as an LCD backlight unit;
    • FIGS. 6-9 are diagrams depicting possible spatial configurations of extraction elements; and
    • FIGS. 10-14 are diagrams depicting possible surface configurations of extraction elements.
    DETAILED DESCRIPTION
  • Methods are described to form light-extracting nanostructures, or other nanostructures, in a polymer replication process, a direct deposition of nanoparticles, or other processes to make a light extraction film for OLED devices. The multifunctional film product can, in addition to enhancing light extraction, serve additional functions such as a substrate, encapsulant, barrier layer, filter, polarizer, or color converter and may be employed either during or after manufacture of an OLED device. The film construction is based upon photonic crystal structures, or other nanostructures, for improved efficiency of light extraction from the devices by modifying the interface between high and low index layers within the device.
  • Elements of the invention include the provision of structures of dimensions comparable to or less than the wavelength of the light to be controlled, the provision of a material with contrasting index of refraction to fill in the areas surrounding the structures and also to planarize the structure in order to present an essentially smooth surface to come in contact with the OLED structure, and the location of this index-contrasting nanostructured layer within a small enough distance from the light-emitting region to be effective in extracting the light that would otherwise be trapped in that region.
  • Light incident from a high index material onto an interface with a lower index medium will undergo total internal reflection (TIR) for all incidence angles greater than the critical angle θC, defined by θC = sin-1 (n2/n1), where n1 and n2 are the refractive indices of the high- and low index regions, respectively. The electromagnetic field associated with this light reflected by TIR extends into the lower-index region in an evanescent standing wave, but the strength of this field diminishes exponentially with distance from the interface. Absorbing or scattering entities located within this evanescent zone, typically about one wavelength thick, can disrupt the TIR and cause the light to pass through the interface. Therefore, it is preferable that the nanostructured index contrast layer be located within the evanescent zone if it is to be most effective in causing extraction of the light from the emission region by scattering or diffraction. Alternatively, the nanostructured index contrast layer need only be in optical communication with a light emitting region of the self-emissive light source when the optical film is located against the self-emissive light source. The term "optical communication" means that a significant or substantial portion of the generated optical field from the light source is capable of reaching the scattering particles or nanostructure.
  • Replication master tools can be fabricated with regular or random structures of the required average periodicity for light extraction, 200 nanometers (nm)-2000nm, over increasingly larger areas. Combining this tooling capability with microreplication processes such as continuous cast and cure (3C) enable the formation of the photonic crystal structures, or other nanostructures, on the surface of a film substrate. Examples of a 3C process are described in the following patents: U.S. Patent Nos. 4,374,077 ; 4,576,850 ; 5,175,030 ; 5,271,968 ; 5,558,740 ; and 5,995,690 .
  • The terms "nanostructure" or "nanostructures" refers to structures having at least one dimension (e.g., height, length, width, or diameter) of less than 2 microns and more preferably less than one micron. Nanostructure includes, but is not necessarily limited to, particles and engineered features. The particles and engineered features can have, for example, a regular or irregular shape. Such particles are also referred to as nanoparticles.
  • The term "nanostructured" refers to a material or layer having nanostructures.
  • The term "photonic crystal structures" refers to periodic or quasi-periodic optical nanostructures interspersed with a material of sufficiently different index of refraction that will enable the structure to produce gaps in the spectrum of allowed electromagnetic modes in the material.
  • The term "index" refers to index of refraction.
  • The term "backfill" refers to the material incorporated into a structure, and of a different index from the structure, to fill in voids in the structure and planarize the structure.
  • The term "extraction elements" refers to any type and arrangement of nanostructures enhancing light extraction from self-emissive light sources. The extraction elements are not contained within a volume distribution.
  • Bottom Emitting OLED Display Device
  • FIG. 1 illustrates a structure of bottom emitting OLED device 100 having a light extraction film. A bottom emitting OLED device is defined as an OLED device emitting light through the substrate. Table 1 describes the exemplary elements of device 100 and the arrangement of those elements, as identified by the reference numbers provided in FIG. 1. Each layer of device 100 can be coated on or otherwise applied to the underlying layer.
    Table 1 - Bottom Emitting OLED Device with Light Extraction Film
    Ref. No. Type of Element
    102 electrode 1
    104 organic layers
    106 electrode 2
    108 high index structure
    110 low index structure
    112 optional barrier layer
    114 substrate
    115 optional functional layers
    116 light extraction film
  • The substrate 114 is composed of a material, substantially transparent (transmissive) to the desired emitted wavelengths, that provides sufficient mechanical support and thermal stability for the device. Substrate 114 preferably comprises a flexible material. Examples of substrate materials include the following: glass; flexible glass; polyethylene terephthalate ("PET"); polyethylene naphthalate ("PEN"); or other translucent or transparent materials. Substrate 114 can optionally also function as a barrier layer. Also, substrate 114 can optionally contain dyes or particles, and it can be tentered or include prismatic structures.
  • The optional barrier layer 112 effectively blocks or helps prevent permeation of oxygen and water to the layers of the device, particularly the organic layers. Examples of barrier layers are described in U.S. Patent Application Publication Nos. 2006/0063015 (describing boron oxide layers with inorganic barrier layers) and 2007/0020451 (describing diamond-like glass (DLG) and diamond-like carbon (DLC)).
  • The electrodes 102 and 106 can be implemented with, for example, transparent conductive oxide (TCO) such as indium tin oxide (ITO) or metals with the appropriate work function to make injection of charge carriers such as calcium, aluminum, gold, or silver.
  • The organic layers 104 can be implemented with any organic electroluminescent material such as a light-emitting polymer, an example of which is described in U.S. Patent No. 6,605,483 . Other examples of suitable light emitting materials include evaporated small molecule materials, light-emitting dendrimers, molecularly doped polymers, and light-emitting electrochemical cells.
  • The light extraction film 116 in this embodiment is composed of substrate 114, optional barrier layer 112, low index structure 110, and high index structure 108. The high index structure uses a backfill medium to effectively provide a planarizing layer over the low index structure in order to make the light extraction film sufficiently planar to allow OLED fabrication. The backfill layer can alternatively have other optical properties. Also, the backfill layer material can function as a barrier to moisture and oxygen or provide electrical conduction, possibly in addition to having barrier properties, depending upon the type of material used. The backfill layer can alternatively be implemented with an optically clear adhesive, in which case the extraction film can be applied to top emitting OLED device, for example. A stabilization layer can optionally be coated on the device before applying the backfill layer.
  • The low index structure 110 has a material with an index substantially matched to the underlying layer, typically the substrate. The low index structure 110 is composed of a nanostructured layer, which can have a periodic, quasi-periodic, or random distribution or pattern of optical nanostructures, including photonic crystal structures. It includes discrete nanoparticles. The nanoparticles can be composed of organic materials or other materials, and they can have any particle shape. The nanoparticles can alternatively be implemented with porous particles. The distribution of nanostructures can also have varying pitches and feature size. At least a portion of the extraction elements or nanostructures are preferably in contact with the flexible substrate, and the extraction elements may have voids beneath them. The layer of nanoparticles can be implemented with nanoparticles in a monolayer, with a layer having agglomerations of nanoparticles, or in a multi-layer.
  • In some embodiments, the addition of small SiO2 nanoparticles to suspensions of larger SiO2 nanoparticles for low index structure 110 can significantly improve the uniformity of the larger nanoparticles in coatings made from the suspension. For example, low index structure 110 can include the additional of 5nm diameter SiO2 nanoparticles in coatings made from suspensions of 440nm diameter SiO2 nanoparticles. These small and large nanoparticles can be surface treated or non-treated. The large nanoparticles can comprises two or more different sizes of large nanoparticles. The large nanoparticles have diameters in the range of 60nm to 10 microns, preferably 100nm to 1 micron, or more preferably 100nm to 500nm. The small nanoparticles have diameters in the range of 3nm to 50nm. The nanoparticles can comprise one or more of the following: metal oxide particles; organic polymer particles; metal particles; or composite particles.
  • Using a distance of the nanostructures on the order of the evanescent wave from the organic layers can result in coupling of the evanescent wave to the nanostructures for extraction of additional light from the device. This coupling preferably occurs when the light extraction film is adjacent to the light emitting region of the self-emissive light source. When the backfill layer has a lower index than the structured layer, then the backfill layer preferably has a thickness substantially equal to the extraction elements. When the backfill layer has a higher index than the structured layer, then the backfill layer can be thicker than the extraction elements provided it can still interact with the evanescent wave. In either case, the structured layer and backfill layer are preferably in sufficient proximity to the light output surface in order to at least partially effect the extraction of light from that surface.
  • The nanostructured features in layer 110 can be fabricated using any printing techniques for replication of submicron features such as the following: imprinting; embossing; nanoimprinting; thermal- or photo-nanoimprint lithography; injection molding; or nanotransfer printing. Another technique for fabricating the extraction elements is described in Example 18 in U.S. Patent No. 6,217,984 .
  • The high index structure 108 is a high index material providing index contrast to the adjacent low index nanostructured layer and provides an effective planarization layer to it. The index of refraction mismatch between nanostructured layer 110 and backfill medium 108 at the emission wavelength(s) is referred to as Δn, and a greater value of Δn generally provides better light extraction. The value of Δn is greater than or equal to 0.3, preferably greater than or equal to 0.4, 0.5, or 1.0. Any index mismatch between the extraction elements and backfill medium will provide for light extraction; however, a greater mismatch tends to provide greater light extraction and is thus preferred. Examples of suitable materials for backfill medium 108 include the following: high index inorganic materials; high index organic materials; a nanoparticle filled polymer material; silicon nitride; polymers filled with high index inorganic materials; and high index conjugated polymers. Examples of high index polymers and monomers are described in C.Yang, et al., Chem.Mater. 7, 1276 (1995), and R.Burzynski, et al., Polymer 31, 627 (1990) and U.S. Patent No. 6,005,137 . Examples of polymers filled with high index inorganic materials are described in U.S. Patent No. 6,329,058 . The backfill layer can be applied to form the planarizing layer using, for example, one of the following methods: liquid coating; vapor coating; powder coating; or lamination.
  • Functionality can be added to the construction by depositing on it a transparent conductor such as ITO (n ≈ 1.9-2.1) with high index, high transparency and low sheet resistivity, to serve as the anode for the OLED device. The ITO can even be used as the backfill for the structure, if the layer can fill the structures and form into a smooth layer without adverse effects on the optical or electrical properties. Alternatively, after backfilling and smoothing, alternating metallic and organic layers may be deposited to form a transparent conductive overlayer (on the backfill layer) in the manner as described in U.S. Patent Application Publication No. 2004/0033369 .
  • Additional flexibility in the functionality of the extractor pattern of the photonic crystal structures or nanostructures can be obtained through the use of photonic quasicrystal structures. These quasicrystal structures are designed using tiling rules; they have neither true periodicity nor translation symmetry but have a quasi-periodicity with long-range order and orientation symmetry, examples of which are described in the following reference: B. Zhang et al., "Effects of the Artificial Ga-Nitride/Air Periodic Nanostructures on Current Injected GaN-Based Light Emitters," Phys.Stat.Sol.(c) 2(7), 2858-61 (2005). The photonic quasicrystal structures offer the possibility of a pseudogap for all propagation directions, and they exhibit unique light scattering behaviors. In particular, these patterns of quasiphotonic crystal structures can eliminate artifacts resulting from the regularity of conventional photonic crystal structures, and they can be used to tailor unique light emission profiles and possibly can eliminate undesirable chromatic effects when working with broadband OLED emitters. Photonic crystal structures are described in the following patents: U.S. Patent Nos. 6,640,034 ; 6,901,194 ; 6,778,746 ; 6,888,994 ; 6,775,448 ; and 6,959,127 .
  • Embodiments can involve the incorporation of the diffractive or scattering nanostructures into a film product which could be continuously produced, for example, on a web line having a polymer film or ultrabarrier coated film substrate fed to a 3C replication process followed by deposition of a high index backfill medium. Alternate ways to incorporate the diffractive or scattering nanoparticles into the film include solution coating a dispersion of particles. This film can be designed to be used directly as the substrate on which a bottom emitting OLED is fabricated, enabling the production of a film capable of many uses in addition to enhancing light extraction.
  • Additional functionality could be incorporated into the light extraction film product by forming the extraction structures on an optional ultrabarrier film, which provides excellent moisture and oxygen barrier properties. Ultrabarrier films include multilayer films made, for example, by vacuum deposition of two inorganic dielectric materials sequentially in a multitude of layers on a glass or other suitable substrate, or alternating layers of inorganic materials and organic polymers, as described in U.S. Patent Nos. 5,440,446 ; 5,877,895 ; and 6,010,751 .
  • Materials may also be incorporated within the film to enhance light extraction through scattering or to filter, color shift, or polarize the light. Finally, surface coatings or structures, for example functional layers 115, can be applied to the air surface of the light extraction film in order to further increase the functionality and possibly value of a light extraction film. Such surface coatings can have, for example, optical, mechanical, chemical, or electrical functions. Examples of such coatings or structures include those having the following functions or properties: antifog; antistatic; antiglare; antireflection; antiabrasion (scratch resistance); antismudge; hydrophobic; hydrophilic; adhesion promotion; refractive elements; color filtering; ultraviolet (UV) filtering; spectral filtering; color shifting; color modification; polarization modification (linear or circular); light redirection; diffusion; or optical rotation. Other possible layers to be applied to the air surface include a barrier layer or a transparent electrically conductive material.
  • Top Emitting OLED Display Device
  • FIG. 2 illustrates a structure of top emitting OLED device 120 with a film substrate having a light extraction film. Table 2 describes the exemplary elements of the device 120 and the arrangement of those elements, as identified by the reference numbers provided in FIG. 2. Each layer of the device can be coated on or otherwise applied to the underlying layer. The configurations shown in FIGS. 1 and 2 are provided for illustrative purposes only, and other configurations of bottom emitting and top emitting OLED display devices are possible.
    Table 2 - Top Emitting OLED Device with Light Extraction Film
    Ref. No. Type of Element
    121 optional functional layers
    122 substrate 1
    124 optional barrier layer
    126 low index structure
    128 high index structure
    130 optical coupling layer
    132 electrode 1
    134 optional thin film encapsulant layer
    136 organic layers
    138 electrode 2
    140 substrate 2
    142 light extraction film
  • The light extraction film 142 in this embodiment is composed of substrate 122, optional barrier layer 124, low index structure 126, and high index structure 128. Low index structure 126 and high index structure 128 can be implemented with the exemplary materials and constructions described above. Layers 128 and 130 can optionally be implemented with a single layer. The substrates 122 and 140, optional barrier layer 124, electrodes 132 and 138, and organic layers 136 can be implemented with the exemplary materials identified above. Substrate 140 can also be optionally implemented with an opaque material such as a metal foil.
  • Optional thin film encapsulant 134 can be implemented with, for example, any suitable material for protecting the organic layers from moisture and oxygen. Examples of encapsulants for OLED devices are described in U.S. Patent No. 5,952,778 and U.S. Patent Application Serial No. 11/424997, filed June 19, 2006 .
  • OLED devices, especially top emitting OLED devices as shown in FIG. 2, are optionally completed by depositing a thin film encapsulant, typically on a semitransparent electrode. This construction of an OLED device provides an advantage; in particular it creates access to the critical high index device-air interface after the completion of device fabrication, enabling a lamination process for the application of the light extraction film. For top emitting OLED devices, embodiments include a light extraction film as described above for bottom emitting OLED devices. Alternatively, the film can be designed to be the capping layer on a top emitting OLED structure when combined with a suitable high index adhesive to serve as the optical layer 130 in order to optically couple the OLED device to the light-extracting layer. The encapsulant material may itself serve as the index contrast material which backfills the nanostructures to form the light extraction layer.
  • OLED Solid State Lighting or Display Element
  • Top emitting OLED device 120 or bottom emitting OLED device 100 can also be used to implement an OLED solid state lighting or display element. In addition to the substrates identified above, examples of substrates useful in top emitting OLED solid state lighting devices, including flexible metal foils, are described in the following papers: D.U. Jin et al., "5.6-inch Flexible Full Color Top Emission AMOLED Display on Stainless Steel Foil," SID 06 DIGEST, pp. 1855-1857 (2006); and A. Chwang et al., ").
  • FIG. 3 is a diagram illustrating a device 220 having spatially modulated OLED devices for use in solid state lighting devices. Device 220 includes a substrate 222 supporting a plurality of OLED devices 223, 224, 225, and 226, each of which may correspond with the structures described above with respect to bottom or top emitting OLED display devices. Each of the OLED devices 223-226 can be individually controlled as represented by lines 228 and 230, which would provide electrical connections to the anodes and cathodes in devices 223-226. Device 220 can include any number of OLED devices 223-226 with electrical connections, and substrate 222 can be scaled to accommodate them. The individual control of devices 223-226, via connections 228 and 230, can provide for spatial modulation of them such that they are individually or in groups lighted in a particular sequence or pattern. Device 220 can be used in solid state light, for example, on a rigid or flexible substrate 222.
  • OLED Backlight Unit
  • FIG. 4 is a diagram of a top emitting OLED backlight unit 180 with light extraction film. Table 3 describes the exemplary elements of the backlight unit 180 and the arrangement of those elements, as identified by the reference numbers provided in FIG. 4. Each layer of backlight unit 180 can be coated on or otherwise applied to the underlying layer. Alternatively, bottom emitting OLEDs can also be used for backlight units.
    Table 3 - OLED Backlight Unit with Light Extraction Film
    Ref. No. Type of Element
    182 polarizer
    184 optional prism layer
    186 optional asymmetric reflective film
    188 optional diffuser
    189 substrate 1
    190 low index structure
    192 high index structure
    194 optical coupling layer
    195 optional thin film encapsulant layer
    197 electrode 1
    200 organic layers
    202 electrode 2
    204 substrate 2
    206 auxiliary optical films
    208 light extraction film
  • The light extraction film 208 in this embodiment is composed of low index structure 190 and high index structure 192. The light extraction film can optionally also include prism layer 184 and diffuser 188. Low index structure 190 and high index structure 192 can be implemented with the exemplary materials and constructions described above. The other elements of this embodiment, as provided in Table 3, can be implemented with the exemplary materials identified above. Layers 192 and 194 can alternatively be implemented with a single layer.
  • FIG. 5 is a diagram illustrating OLED devices used as a liquid crystal display (LCD) backlight unit 242 for an LCD panel 240. Backlight unit 242 may correspond with the structure 180. The backlight unit 242 can alternatively be implemented with the spatially modulated light panel shown in FIG. 3. LCD panel 240 typically includes the entire LCD device except the backlight and drive electronics. For example, LCD panel 240 typically includes the backplane (subpixel electrodes), front and back plates, liquid crystal layer, color filter layer, polarizing filters, and possibly other types of films. Use of OLED devices as a backlight may provide for a thin, low power backlight for LCDs. An example of LCD panel components and a backlight unit are described in U.S. Patent No. 6,857,759 .
  • High Index/Low Index Regions and Surface Configurations
  • FIGS. 6-9 are diagrams depicting the possible spatial configurations of extraction elements. FIG. 6 illustrates a low index structure 250, having a regular pattern of nanostructures, with a high index structure 251 providing a planarizing layer over the nanostructures. The structures 250 and 251 are located between a low index substrate 246 and an OLED device region 247. FIG. 7 illustrates a low index structure 252, having an irregular pattern of nanostructures, with a high index structure 253 providing a planarizing layer over the nanostructures. The structures 252 and 253 are located between a low index substrate 248 and an OLED device region 249. In FIGS. 6 and 7, the low and high index structures are located between a substrate and an OLED device (light emitting) region.
  • FIG. 8 illustrates high index extraction elements 255 within a low index backfill region 254 with the low index region 254 providing the planarizing layer. The extraction elements 255 and backfill 254 are located between a low index substrate 260 and an OLED device region 259. FIG. 9 illustrates low index extraction elements 257 within a high index backfill region 256 with the high index region 256 providing the planarizing layer. The extraction elements 257 and backfill 256 are located between a low index substrate 261 and an OLED device region 262. In the embodiments shown in FIGS. 8 and 9, the extraction elements are concentrated in the evanescent zone. The layers shown in FIGS. 6-9 illustrate patterns and interfaces of the low index and high index structures described above.
  • FIGS. 10-14 are top view diagrams depicting possible surface configurations of extraction elements. FIGS. 10 and 11 illustrate regular periodic arrays of extraction elements. FIG. 12 illustrates a random distribution of extraction elements. FIG. 13 illustrates patterned regions of extraction elements. In particular, FIG. 13 illustrates portions of features, possibly in a regular pattern 264 or an irregular pattern 265, interspersed within a different distribution of features 263. The regular or irregular patterns 264 and 265, respectively, along with the different distribution 263 may each have periodic, quasi-periodic, or random distributions of extraction elements. Such regions of patterns may be useful to optimize extraction of particular wavelengths of light at those regions, for example wavelengths corresponding with red, green, and blue light. In that case, the extraction regions can correspond and be aligned the red, green, and blue regions comprising pixels of a display device, and each extraction region can each be optimized to extract light from the corresponding red, green, and blue regions. FIG. 14 illustrates quasicrystal (tiled patterns) of extraction elements.
  • Examples of techniques for making extraction elements are described in U.S. Patent Application Serial No. 11/556719, filed November 6, 2006 . FIGS. 10-14 illustrate possible surface configurations of the nanostructures or other extraction elements described above with a backfill medium providing the planarizing layer over the nanostructures.
  • Additional techniques, in examples not forming part of the present invention, could include using lithography or interference lithography to expose nanoscale regions in a photosensitive polymer deposited on a flexible polymer web. After the exposure and development steps, the remaining photosensitive polymer would then define a nanostructured surface. Alternatively, this nanostructured photosensitive polymer surface can serve as an etch mask for exposure of the surface in an etching process. This etching technique would transfer the nanoscale pattern into the surface of the underlying polymer web or into a layer of a harder material, such as a silicon oxide, which had been deposited on the polymer web prior to the lithographic steps. The nanoscale surface defined in any of these manners could then be backfilled with an index contrasting medium to form the light scattering or diffracting layer.
  • Distributions of Nanoparticles for Light Extraction (according to the present invention)
  • This embodiment provides enhanced light extraction from an OLED using an index-contrasting film with randomly distributed high index nanostructures created by coating nanoparticles such as, for example, ITO, silicon nitride (Si3N4, referred to here as SiN), CaO, Sb2O3, ATO, TiO2, ZrO2, Ta2O5, HfO2, Nb2O3, MgO, ZnO, In2O3, Sn2O3, AlN, GaN, TiN, or any other high index materials on a substrate used in OLED fabrication or encapsulation, and then applying a low index coating, such as SiO2, Al2O3, DLG, DLC, or polymeric materials over the nanoparticles to provide the index contrast needed for scattering or diffraction efficiency and to planarize the surface. The randomly distributed nanostructures can be in contact with the substrate, proximate the substrate, grouped together in places, or in any random configuration proximate the substrate. A converse construction, potentially providing similar effectiveness, can comprise a random distribution of low index nanoparticles or nanostructures such as SiO2, porous SiO2, Borosilicate (BK), Al2O3, MgF2, CaF, LiF, DLG, DLC, metal particles such as silver or gold particles, poly(methyl methacrylate) (PMMA), polycarbonate, PET, low index polymers, or any other low index materials with a contrasting high index filler material such as vapor deposited Si3N4 or a solvent-coated particle-filled polymer or a high index polymer. The substrate can optionally have one or more of the following coatings: an antistatic coating; or an adhesion promotion coating.
  • Coating processes such as dip coating, knife coating, dye coating, and roll-to-roll coating may be used for distributing the nanoparticles on the surface, and a similar process may be used to coat the backfill/planarization layer. The use of such techniques should render the process simple, easily scaled for manufacturing, and suitable for incorporation in film products manufactured via web line or roll-to-roll processes.
  • The roll-to-roll continuous process fabrication of light extraction films can include assembling monolayer or sub-monolayer coatings of low index nanoparticles on a plastic substrate, the applying an overcoat of high index material. An example of such a roll-to-roll process includes coating bare functionalized silica nanoparticles on plastic (PET) substrates and then overcoating those nanoparticles with a high index backfill material. The high index backfill materials can be obtained by loading epoxy or acrylate polymers with high index nanoparticles such as ZrO2 or TiO2. Additional high index materials are described in U.S. Patent Application Serial No. 12/262393, filed October 31, 2008 .
  • One particular manufacturing method involves applying nanoparticles having a first index of refraction onto a flexible substrate and overcoating a backfill layer on the nanoparticles to form a planarizing layer over them. The backfill layer comprises a material having a second index of refraction different from the first index of refraction. Preferably, a substantial portion of the nanoparticles are within an evanescent zone adjacent to a light emitting region of a self-emissive light source when the optical film is located against the self-emissive light source. For example, a substantial portion of the nanoparticles can be in contact with the substrate to be within the evanescent zone, although in some embodiments the substantial portion of the nanoparticles in the evanescent zone need not be in contact with the substrate.
  • Applying the nanoparticles can involve coating the nanoparticles dispersed in a solvent onto the flexible substrate and allowing the solvent to evaporate before overcoating the backfill layer. Applying the nanoparticles can also involve applying them in dry form to the flexible substrate and then overcoating them with the backfill layer. An alternative to the method involves using substrate with a release agent, in which the particles are applied to a substrate with a release agent, the substrate with the particles is applied to a device substrate with the particles in contact with it, and then the substrate is released to transfer the particles to the device substrate. On particular method involves a single process to coat the substrate with nanoparticles, dry it, coat the backfill layer, dry it again, and then cure the resulting film. Yet another particular method involves a first process to coat the substrate with nanoparticles, dry it, and wind up the coating film, and then a second process to unwind the film, coat the backfill layer, dry it again, and then cure the resulting film.
  • Replication Method (not according to the present invention)
  • One solution for forming a master tool having nanostructures involves the use of interference lithography. Regular periodic features as small as 100nm-150nm can be quickly written using this method. An advantage involves being able to write these patterns over larger areas, which can make the process more amenable to manufacturing.
  • Production of a master tool for replication of the pattern can involve the following. A substrate is coated with an overlayer of photoresist and then illuminated with one or more UV interference patterns to expose the resist in a regular pattern with the desired feature sizes. Development of the resist then leaves an array of holes or posts. This pattern can subsequently be transferred into the underlying substrate through an etching process. If the substrate material is not suitable to be used as a replication tool, a metal tool can be made using standard electroforming processes. This metal replica would then become the master tool.
  • Another method involves forming a master tool having randomly-distributed nanostructures. A solution is prepared comprising nanoparticles of the appropriate size and with the appropriate surface modifications to prevent agglomeration. Methods for preparing such solutions are generally specific to the particular nanoparticles to be dispersed; general methods have been described elsewhere, including U.S. Patent No. 6,936,100 and Molecular Crystals and Liquid Crystals, 444 (2006) 247-255. The solution is then coated onto a flexible substrate using one of a variety of solvent coating techniques, including knife coating, dip coating, spray coating, dye coating, or roll-to-roll coating. Pretreatment of the substrate using methods such as plasma etching may be required in order to assure uniformity of the solution coating. After solvent evaporation, the nanoparticles should be distributed in a way that is microscopically random but macroscopically uniform. As was the case with the uniform tool fabrication process described above, this pattern could then be transferred to an underlying substrate material through an etching or embossing process, or a metal tool can be made using standard electroforming processes.
  • In any of these cases, if a flat master tool has been produced, it or its replicas may then be tiled together to form a larger tool, as described in U.S. Patent No. 6,322,652 , or may be formed into a cylindrical tool for compatibility with a roll-to-roll replication process.
  • Once a master tool has been produced, replication of the structure into a polymer can be done using one of a variety of replication processes, including the 3C process. The substrate for this replication could be any polymer sheeting compatible with the chosen replication process; it may be already coated with the ultrabarrier film as described above. Backfilling would then be performed downstream in, for example, a chemical vapor deposition (CVD) or sputtering process which can deposit a high index material, such as SiN or ITO, which is capable of filling the structures and then leveling out into a smooth layer. If SiN is used, this might then be followed by an ITO deposition process if a conductive upper layer is required. Alternatively, the downstream backfilling may be performed in a solvent coating process using suitable materials.
  • Examples Example 1: 190 nm SiO2 Nanoparticles with No 5 nm SiO2 Nanoparticles (Comparative Example)
  • Dispersions of spherical silica nanoparticles with nominal diameter of 190 nm were obtained from the Nissan Chemical, 10777 Westheimer, Suite 830, Houston, TX 77042, U.S.A. The nanoparticles were treated with polyethylene oxide (PEO and dialyzed, 142971-86-4, 190 nm silica with PEO covered and dialyzed, 33.6% solids).
  • The process details of treated 190 nm SiO2 nanoparticles with PEO are as follows. 363 grams of Nissian MP-4540 (100 grams of silica) was added to a reaction vessel along with 7.5 grams of A1230 polyethylene oxide silane from Momentive Performance Chemicals. The mixture was reacted for 16 hours at 80°C. The reaction mixture was then dialyzed to remove any unreacted silane and other impurities. The solution was place in a 2 Spectra/Por Dialysis membrane having a MWCO (Molecular Weight Cut-Off) of 12-14,000. The material was dialyzed for 24 hours against constantly flowing tap water.
  • The resulting nanoparticle suspension was diluted in 1 methoxy 2 propanol to produce suspensions having 2 percent by weight solids content. The 190 nm SiO2 nanoparticle solution was coated on a PET substrate by a dip coating (coating speed: 65mm/min). It was shown from SEM images that there was a de-wetting issue resulting in regions of the substrate having no particle coating.
  • Example 2: Improved Coating of 190 nm SiO2 Nanoparticles Via Addition of 5 nm SiO2 Nanoparticles (Treated)
  • A 2wt% suspension of 190 nm SiO2 nanoparticles was prepared as described in Example 1, but with the addition of 1.1 wt% of 5 nm SiO2 (treated by PEO: 147426-45-01,5 nm silica particles treated with Silquest A1230). The 190 nm SiO2 nanoparticles were coated on a PET substrate by a dip coating (coating speed of 65 mm/min as in Example 1). Through comparison of SEM images from Example 1 and this sample, the uniformity of the coating was shown to have been improved by adding the small nanoparticles, although the de-wetting of the nanoparticles coating had not completely disappeared.
  • Example 3: Improved Coatings of 190 nm SiO2 Nanoparticles Via Addition of Unmodified 5 nm SiO2 Nanoparticles
  • A 2 wt% of 190 nm SiO2 nanoparticles was prepared as described as in Example 1, but with the addition of 1.1 wt% of 5 nm SiO2 (unmodified small 5 nm SiO2 nanoparticles from Nalco Company, Nalco 2326). It was clearly shown from SEM images that unmodified small SiO2 nanoparticles can significantly improve the large nanoparticle coating uniformity.
  • Example 4: 190nm SiO2 Nanoparticles with 5 nm Modified SiO2 Nanoparticles (Modified with Isooctyltrimethoxysilane and Methyltrimethoxysilane)
  • A 2wt % of 190 nm SiO2 nanoparticles was prepared as described as in Example 1, but with the addition of 1.1 wt% of 5 nm SiO2 nanoparticles modified with isooctyltrimethoxysilane and methytrimethoxysilane. (The 5 nm nanoparticle powder was first dissolved in isopropanol to produce suspensions having 10 percent by weight solids content). As was shown through SEM images, the coating uniformity was improved, although the de-wet of the nanoparticles coating had not completely disappeared.
  • Example 5a: 440 nm SiO2 Nanoparticles Coated by Roll-to-Roll Process without Small Nanoparticles (Comparative Example for Example 5b)
  • Dispersions of spherical silica nanoparticles with nominal diameter of 440 nm were obtained from the Nissan Chemical (Houston Office (Chemical Business), 10777 Westheimer, Suite 830, Houston, TX 77042, U.S.A.. The nanoparticle solution was diluted in 1 methoxy 2 propanol to produce a suspension having 5 percent by weight solids content. The 440 nm SiO2 nanoparticles were coated on a corona-treated PET film (6-8mil thickness) by roll-to roll-process using a 5 mil coating gap (web speed of 10 fpm, ind. pump speed of 1.2 cc/min). The resulting coating was first dried in air at room temperature, then subsequently further dried at 180°F.
  • Example 5b: 440nm SiO2 Nanoparticles Coated by Roll-to-Roll Process with Small Nanoparticles
  • 2.5 wt% of 440 nm SiO2 nanoparticles were prepared as in Example 5a, but then 1 wt% of modified 5 nm SiO2 nanoparticles, prepared as in the Example 2, was added. The 440 nm SiO2 nanoparticles were coated on the corona-treated PET film using the same conditions as in Example 5a.
  • Materials for Examples 6 and 7
  • Materials used in the Examples included silica nanoparticles of 93 nm nominal diameter obtained from the Nalco company, and dodecylbenzenesulfonic sodium salt (DS-10) surfactant obtained from Aldrich. Using these materials with different coating conditions, close-packed monolayers of nanoparticles, or sparse discontinuous layers, could be achieved.
  • Mono-layers of bare silica nanoparticles coated directly on a PET substrate for Examples 6 and 7
  • A silica nanoparticle dispersion produced by diluting a 2 wt% nanoparticles dispersion in H2O to 1 wt% nanoparticles with DS-10 was coated on a corona-treated PET film (6-8 mil thickness) by the roll-to-roll process using a 5 mil gap (web speed of 10 fpm, dispersion delivery rate of 3 cc/min). The coating was dried in air at room temperature, and then subsequently it was further dried at 180°F. It was shown through a SEM photo of the resulting nanoparticle that a uniform and close-packed monolayer of silica nanoparticles was produced.
  • Discontinuous layer of bare silica nanoparticles coated directly on PET substrate for Examples 6 and 7
  • Silica nanoparticle dispersion as above was coated on corona-treated PET film (6-8 mil thickness) by the roll-to-roll process with a 5 mil gap and lower dispersion delivery rate (web speed of 10 fpm, dispersion delivery rate of 1.5 cc/min). The resulting coating was dried in air at room temperature, and subsequently further dried at 180°F on the web.
  • Example 6: Light-Extracting OLED Substrate with Silicon Nitride Overcoated Nanoparticles
  • In order to quantitatively evaluate the OLED efficiency enhancement due to the nanoparticle, 300 nm Si3N4 layer was applied over the silica nanoparticle coating using plasma-enhanced chemical vapor deposition (PECVD, Model PlasmaLab System100 available form Oxford Instruments, Yatton, UK). Conditions used in the Si3N4 deposition are shown in Table 4.
    Table 4 - Conditions Used for Depositing S3iN4 Layer
    Reactant/Condition Value
    SiH4 400 sccm
    NH3 20 sccm
    N2 600 sccm
    Pressure 650 mTorr
    Temperature 60°C
    High frequency (HF) power 20 W
    Low frequency (LF) power 20 W
  • The refractive index of the Si3N4 overcoating was measured using a Metricon Model 2010 Prism Coupler and was found to be 1.7. At the completion of the PECVD process, a low index scattering center with high index backfilling film had been generated.
  • Next, 110 nm of ITO was deposited on the silicon nitride through a 5 mm x 5 mm pixilated shadow mask to serve as the OLED anode. Subsequently, a simple green organic emitting layer and cathode were deposited to complete the OLED. The OLEDs were fabricated by standard thermal deposition in a bell-jar vacuum system. The OLED layers were deposited through a 40 mm x 40 mm shadow mask covering the 5 mm x 5 mm ITO pixels in the following order: TNATA:FeCl3 (3000A, 5% FeCl3)/NPD(400A)/Alq:C545T(300A, 2%)/Alq(200A)/7ALiF/Al.
  • The 5 mm x 5 mm shadow mask was then realigned, and 250 nm of Al metal was deposited to form the cathodes contacting the tops of the pixels. This process provided OLED devices containing several independently addressable 5 mm x 5 mm pixels with 4 pixels disposed over nanoparticles.
  • Electroluminescence measurements showed enhanced OLED light extraction from the nanoparticle coated pixels. An improvement of 50% at current densities between 2-20 mA/cm2 was shown with this modification.
  • Example 7: Light Extracting OLED Substrate having Nanoparticles Overcoated by High Index Polymer Applied in Roll-to-Roll Process.
  • 50-60 wt% of 10 nm ZrO2 nanoparticles (refractive index of 1.85) were dispersed in acrylate to form a high refractive index (1.68) backfill polymer (obtained from Brant U. Kolb, 145840-77-38F). This high index polymer was mixed with 1 methoxy 2 propanol (10 wt%) and was then coated over the nanoparticles previously coated on PET by a roll-to-roll process with a 5 mil gap (web speed of 10 fpm, dispersion delivery rate of 1.6 cc/min). The resulting coating was dried in air at room temperature; subsequently, it was further dried at 180°F on the web. The target thickness of the high index polymer was 300 nm; SEM images indicated an actual thickness of about 300 nm in excellent agreement with the target thickness. The surface of the roll-to-roll coating was shown to be very smooth compared with Si3N4 deposited by plasma enhanced chemical vapor deposition.
  • Example 8: 93nm SiO2 nanoparticles coated by roll-to-roll process with 60nm SiN overcoated on NPs as a stabilization layer Preparation of nanopaticle coating by roll-to-roll process
  • Dispersions of 93nm silica nanoparticles were obtained from the Nalco company. Polyvinyl alcohol (PVA, 98 mole % hydrolyzed, MW 78000) was obtained from Polysciences, Inc., and was dissolved in water with 1wt % solid content for the related experiments. Dodecylbenzenesulfonic sodium salt (DS-10) surfactant was obtained from Alderich.
  • A silica nanoparticle (NP) dispersion solution (93nm, 1wt%, 0.1-lwt% DS-10) was coated on PET film (6-8mil thickness) by a roll-to-roll process using a 5 mil gap (web speed of 10 fpm, dispersion delivery rate of 3 cc/min). The coating was dried in air at room temperature, and then subsequently it was further dried at 180°F.
  • Preparation of 60nm SiN stabilization layer by plasma-enhanced chemical vapor deposition
  • The silica-nanoparticle-coated film was then over-coated with a 60nm thick layer of silicon nitride by plasma-enhanced chemical vapor deposition (PECVD), for stabilization of the NPs (PECVD, Model PlasmaLab™ System100 available form Oxford Instruments, Yatton, UK). The parameters used in the PECVD process are described in Table 5.
    Table 5 - Conditions used for depositing SiN layer
    Reactant/Condition: Value:
    SiH4 400 sccm
    NH3 20 sccm
    N2 600 sccm
    Pressure 650 mTorr
    Temperature
    100°C
    High frequency (HF) power 20W
    Low frequency (LF) power 20W
  • The refractive index of the SiN core layer was measured using a Metricon Model 2010 Prism Coupler, and was found to be 1.7.
  • Preparation of High-RI Coating Using 50 nm TiO2 and ZrO2 Nanoparticles
  • In a glass jar, 4.5 g of ZrO2 HIHC prepared as above, 6.78 g of 50 nm TiO2 dispersion, 24.4 g of 2-butanone, 16.62 g of 1-methoxy-2-propanol were mixed together. The mixture was stirred to form a homogenous white coating solution. The coating solution was applied on above sample (60nm SiN on 93nm nanoparticles/PET) using spin-coating at 4000 rpm for 40 seconds (Karl Suss spin coater, spin coater model CT62 fro Suss MicroTec, Inc.), resulting in transparent high-index coatings. The coatings were cured using a Fusion UV-Systems Inc. Light-Hammer 6 UV (Gaithersburg, Maryland) processor equipped with an H-bulb, operating under nitrogen atmosphere at 100% lamp power at a line speed of 30 feet/min (2 pass). The thickness of the high-index coating was measured to be approximately 150-200 nm. The refractive index of the high index coating is measured as 1.85 using Metricon Prism Coupler.
  • At the completion of the TiO2-polymer backfill coating, a light extraction layer containing the low-index scattering nanostructure planarized with the high-index backfill was produced.
  • Fabrication of OLED
  • Approximately 110nm-thick ITO was deposited onto the backfill-coated NPs structures through a 5mm x 5mm pixilated shadow mask to define the anode geometry. Subsequently, a simple green organic emitting layer and cathode were deposited to complete the OLED. The OLEDs were fabricated by standard thermal deposition in a vacuum system at base pressure of ca. 10-6 Torr. The following OLED construction was deposited: HIL(300nm)/HTL(40nm)/EML(30nm,6%)/Alq(20nm)/ LiF(1nm)/Al(200nm). After completion, the OLED was encapsulated with 3M encapsulation barrier film employing SAES getter as a desiccant and oxygen scavenger in between the encapsulation film and the OLED cathode.
  • The 5mm x 5mm shadow mask was then realigned, and 200nm of Al metal was deposited to form the cathodes contacting the tops of the pixels. This process provided OLED devices containing several independently addressable 5mm x 5mm pixels with 4 pixels disposed over nanoparticles.
  • Electroluminescence measurements showed enhanced OLED light extraction from the nanoparticle coated pixels. An improvement of 50-100% was shown with this modification.

Claims (5)

  1. A multifunctional optical film for enhancing light extraction from a self-emissive light source having a light output surface, comprising:
    a flexible substrate (114, 122, 189, 260, 261) comprising a substantially optically transmissive material;
    a structured layer (110, 126, 190) of extraction elements (255, 257) having a first index of refraction on the flexible substrate (114, 122, 189, 260, 261), wherein the extraction elements (255, 257) are not contained within a volume distribution,
    wherein a substantial portion of the extraction elements (255, 257) are in optical communication with a light emitting region of the self-emissive light source when the optical film is located against the self-emissive light source, and
    wherein the extraction elements (255, 257) having the first index of refraction comprise first nanoparticles of a first size and second nanoparticles of a second size different from the first size, wherein the first size of the first nanoparticles is a diameter in the range of 60 nm to 10 microns, and the second size of the second nanoparticles is a diameter in the range of 3 nm to 50 nm; and
    a backfill layer (108, 128, 192, 254, 256) comprising a material having a second index of refraction different from the first index of refraction, wherein the backfill layer (108, 128, 192, 254, 256) forms a planarizing layer over the extraction elements (255, 257) to present an essentially smooth surface to come into contact with the self-emissive light source, wherein a mismatch between the first index of refraction and the second index of refraction is greater than, or equal to 0.3,
    wherein the structured layer (110, 126, 190) and backfill layer (108, 128, 192, 254, 256) are arranged to be in sufficient proximity to the light output surface in order to at least partially effect extraction of light from that surface when the optical film is located against the self-emissive light source.
  2. The multifunctional optical film of claim 1, wherein the extraction elements (255, 257) comprise a multi-layer of the nanoparticles.
  3. The multifunctional optical film of claim 1, wherein the substantial portion of the extraction elements (255, 257) are proximate but not in contact with the substrate (114, 122, 189, 260, 261).
  4. The multifunctional optical film of claim 1, further comprising a suitable high index adhesive serving as an optical layer (130) for optically coupling the multifunctional optical film to the self-emissive light source.
  5. A device, comprising a self-emissive light source and the multifunctional optical film of any one of the preceding claims coupled to the self-emissive light source.
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